Fungicidal N-(pyrrolidinoacetyl)-anilines

ABSTRACT

Amino aceto anilides of the formula I shown hereinafter are effective microbicides. They may be used to control fungi on plants or parts of plants or to prevent them from fungi attack.

This is a division of application Ser. No. 039,012 filed on May 14, 1979now U.S. Pat. No. 4,244,962, which is a division of application Ser. No.905,312, filed on May 12, 1978, now U.S. Pat. No. 4,165,381, which inturn was a division of application Ser. No. 726,320, filed on Sept. 24,1976, now U.S. Pat. No. 4.098,895.

The present invention provides compounds of the formula I ##STR1##wherein

R₁ represents a C₁ -C₄ -alkyl group, a C₁ -C₄ -alkoxy group or a halogenatom,

R₂ represents a hydrogen atom, a C₁ -C₃ -alkyl group, a C₁ -C₄ -alkoxygroup or a halogen atom,

R₃ represents a hydrogen atom, a C₁ -C₃ -alkyl group or a halogen atom,

R₄ represents a hydrogen atom or a methyl group, with the proviso thatthe total number of carbon atoms contained by the substituents R₁, R₂,R₃ and R₄ in the phenyl ring does not exceed 8, and

X represents ##STR2##

R₅ represents --COOR', COSR' or ##STR3## wherein each of R', R" and R'"independently represents a methyl or ethyl group,

R₆ represents a hydrogen atom or has a meaning assigned to R₇, albeit anindependent one,

R₇ represents a C₁ -C₆ -alkyl group which is unsubstituted orsubstituted by cyano, hydroxyl or C₁ -C₃ -alkoxy, or a C₃ -C₆ -alkenylgroup which is unsubstituted or substituted by halogen, or elserepresents a C₃ -C₆ -alkynyl or C₃ -C₇ -cycloalkyl group, whilst

R₆ and R₇ together with the nitrogen atom to which they are attached canrepresent a C₂ -C₆ -alkylene or alkenylene group which is unsubstitutedor mono- or polysubstituted by halogen or C₁ -C₃ -alkyl and which cancontain one or two heteroatoms, and salts of the compounds of theformula I with inorganic or organic acids.

By alkyl or alkyl moiety of an alkoxy group are meant the followinggroups, depending on the stated number of carbon atoms: methyl, ethyl,propyl, iso-propyl, butyl, iso-butyl, sec. butyl, tert. butyl, andpentyl and hexyl together with their isomers. By analogy, thisdefinition also applies to the alkylene groups, which together with thenitrogen atom to which they are attached form cyclic amines. An alkylenegroup containing 2 carbon atoms is accordingly an ethylene group andtogether with the nitrogen atom to which it is attached forms anaziridine ring. Alkylene groups containing 2 to 6 carbon atoms formscorresponding cyclic amines with one or more double bonds, depending onthe size of the ring and of the number of heteroatoms which can furtherbe contained in the ring.

Alkenyl is to be understood as meaning for example the following groups:vinyl, propenyl, butenyl, 4-pentenyl. An alkynyl group is chiefly apropargyl group.

Suitable C₃ -C₇ -cycloalkyl groups are: cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl groups.

Within the scope of the present invention, heteroatoms are to beunderstood as meaning oxygen, sulphur and nitrogen atoms. By halogenatoms, which can also be present as substituents of a heterocyclic ringformed by R₆ and R₇, are meant fluorine, chlorine, bromine or iodineatoms.

Examples of inorganic acids are: hydrochloric acid, hydrobromic acid,hydroiodic acid, sulphuric acid, phosphoric acid, phosphorous acid,perchloric acid, nitric acid, methoxysulphuric acid etc.

Examples of organic acids are: acetic acid, trichloroacetic acid, oxalicacid, succinic acid, maleic acid, lactic acid, glycollic acid, aconiticacid, citric acid, benzoic acid, benzenesulphonic acid, methanesulphonicacid.

The foregoing enumerations cited by way of example are not to beinterpreted as implying any limitation thereto. The invention alsoprovides microbicidal compositions which contain a compound of theformula I as active component, and, in addition, a method of combatingfungi and bacteria, which comprises the use of the compounds of theformula I.

ω-Aminoacylanilines containing halogen atoms, alkyl or alkoxy groups inthe ortho-positions of the phenyl ring are already known. Pyrrocain(═1-pyrrolidine-aceto-2',6'-dimethylanilide), which is used as a localanaesthetic, is known from U.S. Pat. No. 2,813,861.

Xylocain (═2-diethylaminoaceto-2',6'-dimethylanilide) is also acommercially available local anaesthetic. [Merck Index, 8th Edition, p.618, (Merck & Co. Inc.]. In South African Pat. No. 74/3766,2-n-butyl-2-tert.butylamino-aceto-2', 6'-dimethylanilide is alsoproposed as an improved preparation for the same purpose.

Primary amino-acyl-2',6'-disubstituted anilides are disclosed in DOS No.2,400,540 as therapeutic compounds with antiarrhythmic properties. Noindications of a microbicidal action on phytopathogenic fungi are given.

The closest comparable substances of this publication, which arereferred to as being preferred, such asN-aminoacetyl-2,6-diethylaniline, N-aminoacetyl-2',6'-diethoxyaniline orN-propyl-N-aminoacetyl-2',6'-dimethylaniline, are ineffective againstpathogens of plant diseases.

The present invention is based on the surprising observation thatcompounds having the structure of formula I possess for practicalpurposes a very advantageous microbicidal spectrum for protectingcultivated plants. Examples of cultivated plants within the scope ofthis invention are: cereals, maize, rice, vegetables, sugar-beet, soya,ground nuts, fruit trees, ornamentals, but primarily vines, hops,cucumber plants (cucumber, marrows, melons), solanaceae, such aspotatoes, tobacco plants and tomatoes, and also banana, cocoa andnatural rubber plants.

With the active ingredients of the formula I it is possible to inhibitor destroy the fungi which occur in plants or parts of plants (fruit,blossoms, leaves, stems, tubers, roots) in these and also related cropsof useful plants, and also to protect from such fungi the parts ofplants which grow later. The active ingredients are effective againstthe phytopathogenic fungi which belong to the following classes:Ascomycates (e.g. Erysiphaceae); Basidiomycetes, chiefly rust fungi;fungi imperfecti (e.g. Moniliales); but especially against the Oomycetesbelonging to the class of the Phycomycetes, such as Phytophthora,Peronospora, Pseudoperonospora, Pythium or Plasmopara. In addition, thecompounds of the formula I possess a systemic action. They can also beused as seed dressing agents for protecting seeds (fruit, tubers,grains) and plant cuttings from fungus infections and fromphytopathogenic fungi which occur in the soil.

One of the preferred subgroups of compound of the formula I comprisesthose compounds wherein R₁ represents a methyl group, R₂ is inortho-position to the amino group and represents a methyl or ethyl groupor a chlorine atom, --X--R₅ possesses the group ##STR4## whilst R₃, R₄,R₆, R₇ and R' are as previously defined. These compounds shall bereferred to as group Ia.

On account of their action, those compounds belonging to group Ia are tobe singled out for special mention is which R₃ represents a hydrogenatom, a methyl group, a chlorine or bromine atom, R₄ represents ahydrogen atom or a methyl group, and R' represents a methyl group,whilst each of R₆ and R₇ independently represents a C₁ -C₃ -alkyl groupwhich is unsubstituted or substituted by C₁ -C₃ -alkoxy, or an allyl orchlorallyl group. This subgroup of compounds shall be referred to asgroup Ib.

A further interesting group of compounds comprises those compounds ofthe formula I in which R₁ represents a methyl or ethyl group, R₂ is inortho-position to the amino group and represents a methyl or ethyl groupor a chlorine atom, R₃ and R₄ represent a hydrogen atom or a methylgroup, R₅ represents one of the groups --COOR' or --CON(R")(R'") andeach of R₆ and R₇ independently represents a C₁ -C₄ -alkyl group or amethoxyethyl group, whilst X, R', R" and R'" are as defined in formulaI. These compounds shall be referred to as group Ic.

A group of compounds which are very effective against phytopathogenicfungi comprises those compounds of the formula I' ##STR5## wherein

R₁ ' represents a methyl or methoxy group,

R₂ ' represents a methyl or ethyl group or a chlorine atom,

R₃ ' represents a hydrogen atom, a methyl group, a chlorine or bromineatom,

R₆ ' represents a methyl, ethyl or n-propyl group, and

R₇ ' represents a methyl, ethyl, n-propyl or isopropyl group.

From the class of the heterocyclic acylanilides, namely those wherein R₆and R₇ together with the nitrogen atom to which they are attached form aring, those compounds of the formula I are to be singled out forparticular mention wherein

R₁ represents a methyl or methoxy group,

R₂ is in ortho-position to the amino group and represents a methyl orethyl group, a chlorine or bromine atom,

R₃ represents a hydrogen atom, a methyl group, a chlorine or bromineatom,

R₄ represents a hydrogen atom or a methyl group, and --X--R₅ representsthe group --CH(CH₃)--COOCH₃ or --CH(CH₃)--COSCH₃, whilst the group--N(R₆)(R₇) represents a 5- or 6-numbered heterocyclic ring which isunsubstituted or mono- or di-substituted by halogen or C₁ -C₃ -alkyl andwhich optionally contains one or two further heteroatoms or noheteroatoms. These compounds shall be referred to as group Id.

Within the heterocyclic acylanilides of the group Id, mention is to bemade of the ring systems formed from the group --N(R₆)(R₇), which can bepartially or completely hydrogenated, or conversely, depending on thestructural possibility, can contain one or more double bonds:piperidine, monomethylpiperidine, dimethylpiperidine, chloropiperidine,dibromopiperidine, pyrimidine, N-methylpyrimidine, pyridazine,morpholine, thiomorpholine, pyrrole, pyrazole, thiazole, thiazolidine,oxazolidine, triazole. Those compounds belonging to group Id, in which--N(R₆)(R₇) forms a pyrazole or 1,2,4-triazole ring, possess a verypronounced microbicidal section. The compounds of group Id which arederived from 1,2,4-triazole are preferred.

Even when used in high concentrations, compounds of the formula I are ingeneral well tolerated by cultivated plants.

According to a further object of the present invention, the compounds ofthe formula I are obtained

(A) by acylating a compound of the formula II ##STR6## with a carboxylicacid of the formula III ##STR7## or with the ester or acid anhydridethereof or with the hydrohalide of its acid halide, or

(B) by initially correspondingly monohaloacylating a compound of theformula II to give an intermediate of the formula IV ##STR8## andoptionally further reacting it with a secondary amine of the formula V##STR9##

In the formulae II, III, IV and V, the symbols R₁ to R₇ and X are asdefined in formula I, whilst Hal' represents a halogen atom, preferablya chlorine or bromine atom.

The reactions can be carried out in the presence or absence of solventsor diluents which are inert to the reactants. Examples of suitablesolvents or diluents are: aliphatic or aromatic hydrocarbons, such asbenzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons,such as chlorobenzene, methylene chloride, ethylene chloride,chloroform; ethers and ethereal compounds, such as dialkyl ethers,dioxane, tetrahydrofurane; nitriles, such as acetonitrile;N,N-dialkylated amides, such as dimethyl formamide; dimethyl sulphoxide;ketones, such as methyl ethyl ketone, and mixtures of such solvents.

The reaction temperatures are between 0° and 180° C., preferably between20° C. and 120° C. It is often advantageous to use acid acceptors orcondensation agents. Suitable examples are: tertiary amines, for exampletrialkylamines (e.g. triethylamine), pyridine and pyridine bases, orinorganic bases, for example the oxides and hydroxides, hydrogencarbonates and carbonates of alkali metals and alkaline earth metals,and sodium acetate. Moreover, in the first process (A) and in themonohaloacetylation of process (B), it is possible to use an excess ofthe respective aniline derivative of the formula II as acid acceptor. Anexcess of a compound of the formula V can also be used as acid acceptorin the further reaction of a compound of the formula IV to give thecompound of the formula I.

Process (A), in which compounds of the formula II are used as startingmaterials, can also be carried out without acid acceptors. On someoccassions it is expedient to introduce nitrogen in order to expel thehydrogen halide that has formed, and on others it is very advantageousto use dimethyl formamide as reaction catalyst.

Particulars on the manufacture of the intermediates of the formula IIcan be inferred from those methods which are generally indicated for themanufacture of anilinoalkanoic acid esters in the following publication:

J.Org. Chem. 30, 4101 (1965); Tetrahedron 1967, 487; Tetrahedron 1967,493.

The compounds of the formula I, in which ##STR10## contain anasymmetrical carbon atom (*) and can be resolved into the opticalantipodes in the customary manner. In this connection, the enantiomericD-form has the more pronounced microbicidal action.

Within the scope of the invention, those compounds, the compositionswhich contain them and their use, which refer to the D-configurations ofthe formula I, are accordingly preferred.

The pure optical D-antipodes are obtained by manufacturing for examplethe racemic compound of the formula VI ##STR11## wherein R₁, R₂, R₃ andR₄ are as defined in formula I, and then reacting it in known mannerwith a nitrogen-containing optically active base to give thecorresponding salt. The pure D-form is obtained stepwise by fractionalcrystallisation of the salt and subsequent liberation of the acid of theformula VI which is enriched with the optical D-antipode and, ifappropriate, repetition (also several times) of the salt formation,crystallisation and liberation of the α-anilino-propionic acid of theformula VI. From this pure D-form it is then possible, if desired, toobtain the optical D-configuration of the ester of the formula II inknown manner, for example in the presence of HCl or H₂ SO₄, withmethanol or ethanol or with methyl mercaptan or ethyl mercaptan (or withthe alkali salts thereof), or else to obtain the amide of the formula IIwith the corresponding amine of the formula HN(R")(R'"), preferably byway of the acid halide. A suitable optically active organic base is forexample α-phenylethylamine.

Instead of fractional crystallisation, it is also possible to obtain theenantiomeric D-form of the formula VII by diazotising the amino group inthe naturally ##STR12## occurring L-alanine in the presence, forexample, of HCl or HBr, and thereby replacing it by halogen accompaniedby the splitting off of M₂ and with retention of the L-configuration,then, if appropriate, effecting esterification with methanol or ethanol,and subsequently reacting the ester with the aniline of the formula VIII##STR13##

when predominantly inversion to the D-configurations of the formula VIIoccurs (J.Am. Chem. Soc. 76, 6065). Accordingly, the thiols (in which R₅=COSR') and the amides in which R₅ =--CON(R")(R'") can also be obtainedin this manner.

Irrespective of the cited optical isomerism, an atropisomerism isobserved about the phenyl--N<axis in those instances in which the phenylring is substituted at least in 2,6-position and at the same timeunsymmetrically to this axis (i.e. optionally also on account of thepresence of additional substituents).

Provided no synthesis with the object of isolating pure isomers iscarried out, a product of the formula I will normally occur as a mixtureof these possible isomers. However, the basically more advantageousfungicidal action of the enantiomeric D-form derived from the formula VI(in comparison with the D,L-form or with the L-form) is retained and isnot noticeably affected by the atropisomerism.

The following Examples will serve to illustrate the invention in moredetail but do not limit it to what is described therein. Unless statedto the contrary, an active substance of the formula I which can occur inoptically active forms is always to be understood as meaning the racemicmixture.

EXAMPLE 1

Manufacture of ##STR14##N-(1'-Methoxycarbonyl-ethyl)-N-diethylaminoacetyl-2,6-dimethylaniline.

(a) Preparation ofN-(1'-methoxycarbonyl-ethyl)-N-chloroacetyl-2,6-dimethylaniline(intermediate). 990.3 g (4.76 g-moles) of methylα-(2,6-dimethylanilino)propionate are mixed with 605 g (5.7 g-moles) ofsodium carbonate in 2.5 liters of absolute benzene. To this mixture areadded 455 ml (5.7 g-moles) of monochloroacetyl chloride so slowly thatthe temperature of the reaction mixture does not exceed 30°-35° C. Afterthe mixture has been stirred overnight at room temperature, it isfiltered and the filtrate is concentrated by rotary evaporation atapprox. 50° C. The residue is recrystallised from benzine (boiling range65°-90° C.) to yield 1132 g of intermediate with a melting point of92°-94° C.

(b) 29 g of the product obtained in (a) and 60 g of diethylamine in 100ml of water are heated for 60 hours to 80° C. The reaction mixture isthen diluted with 200 ml of water, cooled, and extracted with three 200ml portions of ethyl acetate. The combined extracts are washed with asmall amount of water, dried over sodium sulphate and filtered. Theethyl acetate is then evaporated. The crude product is purified bydistillation in a high vacuum, b.p. 138°-140° C./0.05 Torr. The oil canbe crystallised by trituration with petroleum ether. The colourlesscrystals of compound 1.3 melt at 28°-32° C.

The following compounds of the formula Ie can be obtained in this manneror by one of the methods indicated above: ##STR15##

    __________________________________________________________________________     Compound                                                                            R.sub.2                                                                            R.sub.3                                                                           Z.sub.1                                                                                         (temperatures in °C.)Physical                                         constant                                     __________________________________________________________________________    1.1   CH.sub.3                                                                           H   OCH.sub.3                                                                           N(CH.sub.3).sub.2                                                                         m.p. 61-63,5°                         1.2   CH.sub.3                                                                           H   SCH.sub.3                                                                           N(CH.sub.3).sub.2                                                                         m.p. 84-88°                           1.3   CH.sub.3                                                                           H   OCH.sub.3                                                                           N(C.sub.2 H.sub.5).sub.2                                                                  m.p. 28-32°                           1.4   C.sub.2 H.sub.5                                                                    H   N(CH.sub.3).sub.2                                                                   N(CH.sub.3).sub.2                                        1.5   CH.sub.3                                                                           H   OCH.sub.3                                                                           N(n-C.sub.3 H.sub.7).sub.2                                                                b.p. 125°/0.04 Torr.                  1.6   CH.sub.3                                                                           H   SCH.sub.3                                                                           N(n-C.sub.3 H.sub.7).sub.2                                                                b.p. 154°/0.1 Torr.                   1.7   C.sub.2 H.sub.5                                                                    H   N(CH.sub.3).sub.2                                                                   N(n-C.sub.3 H.sub.7).sub.2                               1.8   CH.sub.3                                                                           H   OCH.sub.3                                                                           N(n-C.sub.4 H.sub.9).sub.2                                                                b.p. 190°/0.2 Torr.                   1.9   C.sub.2 H.sub.5                                                                    H   OCH.sub.3                                                                           N(CH.sub.3).sub.2                                        1.10  CH.sub.3                                                                           H   OCH.sub.3                                                                           N(n-C.sub.6 H.sub.13).sub.2                                                               b.p. 180°/0.05 Torr.                  1.11  CH.sub.3                                                                           H   SCH.sub.3                                                                           N(C.sub.2 H.sub.5).sub.2                                 1.12  CH.sub.3                                                                           H   OCH.sub.3                                                                           N(CH.sub.2 CH.sub.2 OCH.sub.3).sub.2                                                      b.p. 160-165°/0.07                                                     Torr.                                        1.13  CH.sub.3                                                                           H   OCH.sub.3                                                                           N(CH.sub.2CHCH.sub.3).sub.2                                                               b.p. 134°/0.05 Torr.                  1.14  C.sub.2 H.sub.5                                                                    H   OCH.sub.3                                                                           N(n-C.sub.3 H.sub.7).sub.2                               1.15  C.sub.2 H.sub.5                                                                    H   OCH.sub.3                                                                           N(C.sub.2 H.sub.5).sub.2                                                                  b.p. 145°/0.05 Torr.                  1.16  CH.sub.3                                                                           H   OCH.sub.3                                                                           N(CH.sub.2 CH.sub.2 OH).sub.2                            1.17  C.sub.2 H.sub.5                                                                    H   OCH.sub.3                                                                            ##STR16##  m.p. 84-87°                           1.18  CH.sub.3                                                                           H   OCH.sub.3                                                                            ##STR17##  m.p. 92-94°                           1.19  C.sub.2 H.sub.5                                                                    H   OCH.sub.3                                                                           N(CH.sub.2CHCH.sub.2).sub.2                              1.20  CH.sub.3                                                                           H   OCH.sub.3                                                                            ##STR18##  b.p. 185°/0.1 Torr.                   1.21  Cl   H   OCH.sub.3                                                                           N(CH.sub.2CHCH.sub.2).sub.2                              1.22  CH.sub.3                                                                           H   SCH.sub.3                                                                           N(CH.sub.2 CH.sub.2 OCH.sub.3).sub.2                                                      b.p. 175°/0.1 Torr.                   1.23  CH.sub.3                                                                           H   OCH.sub.3                                                                            ##STR19##  b.p. 167°/0.2 Torr.                   1.24  Cl   H                                                                                  ##STR20##                                                                          N(n-C.sub.3 H.sub.7).sub.2                               1.25  Cl   H   OCH.sub.3                                                                           N(CH.sub.3).sub.2                                                                         m.p. 85-87°                           1.26  CH.sub.3                                                                           H   OCH.sub.3                                                                           NHtert.C.sub.4 H.sub.9                                                                    b.p. 147°/0.6 Torr.                   1.27  C.sub.2 H.sub.5                                                                    H   OCH.sub.3                                                                           NHtert.C.sub.4 H.sub.9                                                                    b.p. 160°/0.15 Torr.                  1.28  Cl   H   OCH.sub.3                                                                           N(C.sub.2 H.sub.5).sub.2                                 1.29  Cl   H   OCH.sub.3                                                                            ##STR21##  b.p. 180-186°/0.04 Torr.              1.30  C.sub.2 H.sub.5                                                                    H   SCH.sub.3                                                                           N(CH.sub.3).sub.2                                                                         b.p. 161°/0.8 Torr.                   1.31  CH.sub.3                                                                           3-CH.sub.3                                                                        N(CH.sub.3).sub.2                                                                   N(n-C.sub.3 H.sub.7).sub.2                               1.32  CH.sub.3                                                                           4-CH.sub.3                                                                        SCH.sub.3                                                                           N(n-C.sub. 3 H.sub.7).sub.2                                                               b.p. 181°/0.8 Torr.                   1.33  CH.sub.3                                                                           3-CH.sub.3                                                                        SCH.sub.3                                                                           N(CH.sub.3).sub.2                                                                         m.p. 59-61°                           1.34  CH.sub.3                                                                           3-CH.sub.3                                                                        OCH.sub.3                                                                           N(CH.sub.3).sub.2                                                                         b.p. 155°/0.1 Torr.                   1.35  CH.sub.3                                                                           3-Br                                                                              OCH.sub.3                                                                           N(CH.sub.3).sub.2                                                                         b.p. 187°/0.02 Torr.                  1.36  CH.sub.3                                                                           3-CH.sub.3                                                                        OCH.sub.3                                                                           N(CH.sub.3).sub.2                                                                         b.p. 150-155°/0.1                                                      Torr.                                        1.37  CH.sub.3                                                                           3-Br                                                                              OCH.sub.3                                                                           N(n-C.sub.3 H.sub.7).sub.2                               1.38  CH.sub.3                                                                           3-CH.sub.3                                                                        OCH.sub.3                                                                           N(C.sub.2 H.sub.5).sub.2                                                                  b.p. 152°/0.04 Torr.                  1.39  OCH.sub.3                                                                          H   OCH.sub.3                                                                           N(CH.sub.3).sub.2                                        1.40  CH.sub.3                                                                           3-CH.sub.3                                                                        OCH.sub.3                                                                           N(n-C.sub.3 H.sub.7).sub.2                                                                b.p. 172°/0.2 Torr.                   1.41  CH.sub.3                                                                           4-Br                                                                              OCH.sub.3                                                                           N(CH.sub.3).sub. 7                                       1.42  CH.sub.3                                                                           3-CH.sub.3                                                                        OCH.sub.3                                                                           N(CH.sub.2CHCH.sub.2).sub.2                                                               b.p. 160°/0.08 Torr.                  1.43  CH.sub.3                                                                           4-Br                                                                              OCH.sub.3                                                                           N(C.sub.2 H.sub.5).sub.2                                 1.44  CH.sub.3                                                                           4-Br                                                                              OCH.sub.3                                                                           N(n-C.sub.3 H.sub.7).sub.2                               1.45  CH.sub.3                                                                           4-Cl                                                                              OCH.sub.3                                                                           N(n-C.sub.3 H.sub.7).sub.2                                                                b.p. 168°/0.09 Torr.                  1.46  CH.sub.3                                                                           4-Br                                                                              OCH.sub.3                                                                            ##STR22##                                               1.47  C.sub.2 H.sub.5                                                                    4-Br                                                                              OCH.sub.3                                                                           N(CH.sub.3).sub.2                                        1.48  CH.sub.3                                                                           4-Br                                                                              OCH.sub.3                                                                           N(CH.sub.2 CH.sub.2 OCH.sub.3).sub.2                     1.49  C.sub.2 H.sub.5                                                                    4-Br                                                                              OCH.sub.3                                                                           N(nC.sub.3 H.sub.7).sub.2                                1.50  CH.sub.3                                                                           4-CH.sub.3                                                                        OCH.sub.3                                                                           N(CH.sub.3).sub.2                                                                         m.p. 50-51°                           1.51  CH.sub.3                                                                           4-CH.sub.3                                                                        OCH.sub.3                                                                           N(C.sub.2 H.sub.5)                                                                        b.p. 137°/0.07 Torr.                  1.52  CH.sub.3                                                                           4-CH.sub.3                                                                        OCH.sub.3                                                                           N(CH.sub.2CHCH.sub.2).sub.2                                                               b.p. 147°/0.04 Torr.                  1.53  CH.sub.3                                                                           4-CH.sub.3                                                                        SCH.sub.3                                                                           N(CH.sub. 3).sub.2                                                                        m.p. 65-67°                           1.54  CH.sub.3                                                                           H   OCH.sub.3                                                                            ##STR23##  oil                                          1.55  CH.sub.3                                                                           H   OCH.sub.3                                                                            ##STR24##  oil                                          __________________________________________________________________________

and the following compounds of the formula

    ______________________________________                                        1.56                                                                                ##STR25##                oil                                            1.57                                                                                ##STR26##                                                               1.58                                                                                ##STR27##                                                               1.59                                                                                ##STR28##                m.p. 118-120°                           1.60                                                                                ##STR29##                                                               1.61                                                                                ##STR30##                oil                                            ______________________________________                                    

The following compounds of the formula If can be obtained in this manneror by one of the methods indicated above: ##STR31##

    __________________________________________________________________________     Compound                                                                            R.sub.1                                                                          R.sub.2                                                                          R.sub.3                                                                           Z.sub.1                                                                                           Physical constant (temperatures in                                           °C.)                               __________________________________________________________________________    1.62  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H                                                                                  ##STR32##                                                                           CH.sub.2 N(CH.sub.3).sub.2                                                                 m.p.  84-87°                       1.63  CH.sub.3                                                                         Cl H                                                                                  ##STR33##                                                                           CH.sub.2 N(CH.sub.3).sub.2                                                                 m.p. 111-113°                      1.64  CH.sub.3                                                                         CH.sub.3                                                                         H   OCH.sub.3                                                                            CH.sub.2 N(CH.sub.3).sub.2                             1.65  CH.sub.3                                                                         Cl H                                                                                  ##STR34##                                                                           CH.sub.2 N(nC.sub.3 H.sub.7).sub.2                     1.66  CH.sub.3                                                                         CH.sub.3                                                                         H   OCH.sub.3                                                                            CH.sub.2 N(nC.sub.3 H.sub.7).sub.2                     1.67  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H                                                                                  ##STR35##                                                                           CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                          m.p. 108-115°                      1.68  CH.sub.3                                                                         CH.sub.3                                                                         3-CH.sub.3                                                                        OCH.sub.3                                                                            CH.sub.2N(C.sub.2 H.sub.5).sub.2                       1.69  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H                                                                                  ##STR36##                                                                           CH.sub.2 N(C.sub.2 H.sub.5).sub.2                      1.70  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H                                                                                  ##STR37##                                                                           CH.sub.2 N(n-C.sub.3 H.sub.7).sub.2                                                        m.p. 118-126°                      1.71  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H                                                                                  ##STR38##                                                                            ##STR39##                                             1.72  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H                                                                                  ##STR40##                                                                           CH.sub.2 N(CH.sub.2 CHCH.sub.2).sub.2                  1.73  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H                                                                                  ##STR41##                                                                           CH.sub.2 N(CH.sub.2 CH.sub.2 OCH.sub.3).sub.2          1.74  C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                  H   OCH.sub.3                                                                            CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                          m.p. 110-118°                      1.75  CH.sub.3                                                                         CH.sub.3                                                                         H   SC.sub.2 H.sub.5                                                                     CH.sub.2 N(C.sub.2 H.sub.5).sub.2                      __________________________________________________________________________

EXAMPLE 2

Manufacture of ##STR42##N-(1'Methoxycarbonyl-ethyl)-N-morpholinoacetyl-2,6-dimethylaniline.

(a) Preparation ofN-(1'-Methoxycarbonyl-ethyl)-N-chloroacetyl-2,6-dimethylaniline.

990.3 g (4.76 g-moles) of methyl α-(2,6-dimethylanilino)propionate aremixed with 605 g (5.7 g-moles) of sodium carbonate in 2.5 liters ofabsolute benzene. To this mixture are added 455 ml (5.7 g-moles) ofmonochloroacetyl chloride so slowly that the temperature of the reactionmixture does not exceed 30°-35° C. After the mixture has been stirredovernight at room temperature, it is filtered and the filtrate isconcentrated by rotary evaporation at approx. 50° C. The residue isrecrystallised from benzine (boiling range 65°-90° C.) to yield 1132 gof intermediate with a melting point of 92°-94° C.

(b) 29 g of the product obtained in (a) and 44 g of morpholine in 100 mlof water are heated for 20 hours to 100° C. The reaction mixture is thencooled and extracted with two 150 ml portions of toluene. The combinedextracts are washed with a small amount of water, dried over sodiumsulphate and filtered. The solvent is then evaporated. The resultant oilcan be crystallised by trituration with petroleum ether. Afterrecrystallisation from toluene/petroleum ether, compound 2.10 has amelting point of 77°-79° C.

EXAMPLE 3

Manufacture of ##STR43##N-(1'-methoxycarbonyl-ethyl-N-(1,2,4-triazol-1-yl)-acetyl-2,6-dimethylaniline.

In an atmosphere of nitrogen, 20.8 g of 1,2,4-triazole in 100 ml oftetrahydrofurane are added dropwise to 14.4 g of 50% sodium hydride in60 ml of tetrahydrofurane and the reaction mixture is refluxed for 3hours until complete formation of the sodium salt has taken place. Aftercooling to 0° C., 42.5 g ofN-(1'-methoxycarbonyl-ethyl)-N-chloroacetyl-2,6-dimethylaniline in 200ml of tetrahydrofurane are slowly added with stirring. The batch isstirred for 12 hours at room temperature and refluxed for 48 hours.After cooling, 20 ml of water are added in an atmosphere of nitrogen.The mixture is then poured onto ice-water and extracted with three 100ml portions of diethyl ether. The combined extracts are dried oversodium sulphate and filtered. The diethyl ether is evaporated. Afterrecrystallisation from toluene/petroleum ether, compound 2.20 melts at131°-132° C. The following compounds of the formula Ig are obtained inthis manner or by one of the methods indicated above: ##STR44##

    __________________________________________________________________________                                    Physical constant                             Compound                                                                            R.sub.2                                                                            R.sub.3                                                                           Z.sub.1                                                                            Z.sub.2     (temperatures in °C.)                  __________________________________________________________________________    2.1   CH.sub.3                                                                           H   OCH.sub.3                                                                                      m.p. 68-72°                            2.2   C.sub.2 H.sub.5                                                                    H   OCH.sub.3                                                                           ##STR45##  b.p. 153°/0.01 Torr.                   2.3   CH.sub.3                                                                           H   SCH.sub.3                                                                           ##STR46##  viscous                                       2.4   CH.sub.3                                                                           H   OCH.sub.3                                                                           ##STR47##  m.p. 58.5-60°                          2.5   C.sub.2 H.sub.5                                                                    H   OCH.sub.3                                                                           ##STR48##  b.p. 167°/0.6 Torr                     2.6   CH.sub.3                                                                           H   OCH.sub.3                                                                           ##STR49##  b.p. 180°/0.1 Torr                     2.7   CH.sub.3                                                                           H   OCH.sub.3                                                                           ##STR50##  oil                                           2.8   CH.sub.3                                                                           H   OCH.sub.3                                                                           ##STR51##  >300° (decomp.)                        2.9   CH.sub.3                                                                           3-CH.sub.3                                                                        OCH.sub.3                                                                           ##STR52##  oil                                           2.10  CH.sub.3                                                                           H   OCH.sub.3                                                                           ##STR53##  m.p. 77-79°                            2.11  C.sub.2 H.sub.5                                                                    H   OCH.sub.3                                                                           ##STR54##  b.p. 158-162° C./0.4 Torr.             2.12  CH.sub.3                                                                           H   OCH.sub.3                                                                           ##STR55##  b.p. 168-170°/0.5 Torr.                2.13  CH.sub.3                                                                           H   OCH.sub.3                                                                           ##STR56##  b.p. 198°/1.5 Torr.                    2.14  CH.sub.3                                                                           H   OCH.sub.3                                                                           ##STR57##  oil                                           2.15  CH.sub.3                                                                           H   OCH.sub.3                                                                           ##STR58##  b.p. 148-154°/0.02 Torr.               2.16  CH.sub.3                                                                           H   OCH.sub.3                                                                           ##STR59##  oil (viscous)                                 2.17  Cl   H   OCH.sub.3                                                                           ##STR60##  b.p. 175-178°/0.09 Torr.               2.18  CH.sub.3                                                                           H   OCH.sub.3                                                                           ##STR61##  oil                                           2.19  CH.sub.3                                                                           H   OCH.sub.3                                                                           ##STR62##  b.p. 168-172°/0.05                     __________________________________________________________________________                                    Torr.                                     

The following compounds of the formula Ih are obtained in this manner orby one of the methods indicated above: ##STR63##

    __________________________________________________________________________    Com-                        Physical constant                                 pound                                                                             R.sub.1                                                                           R.sub.2                                                                            R.sub.3                                                                           R.sub.4                                                                           R.sub.5                                                                              (temperatures in °C.)                      __________________________________________________________________________    2.20                                                                              CH.sub.3                                                                          CH.sub.3                                                                           H   H   --COOCH.sub.3                                                                        m.p. 131-132°                              2.21                                                                              CH.sub.3                                                                          CH.sub.3                                                                           H   H   --CO--SCH.sub.3                                                                      m.p. 148-151°                              2.22                                                                              CH.sub.3                                                                          CH.sub.3                                                                           3-CH.sub.3                                                                        H   --COOCH.sub.3                                                                        resin                                             2.23                                                                              CH.sub.3                                                                          CH.sub.3                                                                           3-CH.sub.3                                                                        H   --CO--SCH.sub.3                                                                      viscous                                           2.24                                                                              CH.sub.3                                                                          C.sub.2 H.sub.5                                                                    H   H   --COOCH.sub.3                                                                        b.p. 162°/0.01 Torr.                       2.25                                                                              CH.sub.3                                                                          C.sub.2 H.sub.5                                                                    H   H   --CO--SCH.sub.3                                                                      b.p. 148°/0.08 Torr.                       2.26                                                                              CH.sub.3                                                                          CH.sub.3                                                                           4-Cl                                                                              H   --COOCH.sub.3                                                                        m.p. 135-137°                              2.27                                                                              CH.sub.3                                                                          C.sub.2 H.sub.5                                                                    4-Br                                                                              H   --COOCH.sub.3                                                                        m.p. 119-120°                              2.28                                                                              CH.sub.3                                                                          CH.sub.3                                                                           H   H   --COOC.sub.2 H.sub.5                                                                 m.p. 137-139°                              2.29                                                                              CH.sub.3                                                                          H    5-CH.sub.3                                                                        H   --COOCH.sub.3                                                                        m.p. 130-132°                              2.30                                                                              CH.sub.3                                                                          Cl   H   H   --COOCH.sub.3                                                                        m.p. 109-112°                              2.31                                                                              CH.sub.3 O                                                                        CH.sub.3                                                                           H   H   --COOCH.sub.3                                                                        m.p. 150-152°                              2.32                                                                              CH.sub.3                                                                          Cl   H   H   --CO--SCH.sub.3                                                                      viscous                                           2.33                                                                              CH.sub.3                                                                          CH.sub.3                                                                           3-CH.sub.3                                                                        5-CH.sub.3                                                                        --COOCH.sub.3                                                                        m.p. 105-108°                              2.34                                                                              CH.sub.3                                                                          CH.sub.3                                                                           3-CH.sub.3                                                                        5-CH.sub.3                                                                        --CO--SCH.sub.3                                                                      m.p. 123-125°                              2.35                                                                              CH.sub.3                                                                          isoC.sub.3 H.sub.7                                                                 H   H   --COOCH.sub.3                                                                        m.p. 95-98°                                __________________________________________________________________________     The compounds of the formula Ii are also obtained in corresponding manner:     ##STR64##

    __________________________________________________________________________                                Physical constant                                 Compound                                                                            R.sub.1                                                                          R.sub.2                                                                          R.sub.3                                                                           R.sub.4                                                                           R.sub.5 (temperatures in °C.)                      __________________________________________________________________________    2.36  CH.sub.3                                                                         CH.sub.3                                                                         H   H   --COOCH.sub.3                                                                         b.p. 175°/0.01 Torr.                       2.37  CH.sub.3                                                                         CH.sub.3                                                                         3-CH.sub.3                                                                        H   --COOCH.sub.3                                                                         b.p. 147°/0.006 Torr.                      2.38  CH.sub.3                                                                         CH.sub.3                                                                         3-CH.sub.3                                                                        5-CH.sub.3                                                                        --COOCH.sub.3                                                                         b.p. 158°/0.003 Torr.                      2.39  CH.sub.3                                                                         CH.sub.3                                                                         H   H   --CO--S--CH.sub.3                                                                     viscous                                           __________________________________________________________________________     The following compounds of the formula Ij are also obtained in this manner     or by one of the methods indicated above:     ##STR65##

    __________________________________________________________________________                                Physical constant                                 Compound                                                                            R.sub.1                                                                           R.sub.2                                                                          R.sub.3                                                                           R.sub.4                                                                           R.sub.5                                                                              (temperatures in °C.)                      __________________________________________________________________________    2.40  CH.sub.3                                                                          CH.sub.3                                                                         H   H   --COOCH.sub.3                                                                        n.sub.D.sup.22 1.5222                             2.41  CH.sub.3                                                                          CH.sub.3                                                                         H   H   --COSCH.sub.3                                                                        viscous                                           2.42  CH.sub.3                                                                          CH.sub.3                                                                         3-CH.sub.3                                                                        H   --COOCH.sub.3                                                                        viscous                                           2.43  CH.sub.3                                                                          CH.sub.3                                                                         3-CH.sub.3                                                                        5-CH.sub.3                                                                        --COOCH.sub.3                                                                        b.p. 162°/0.001 Torr.                      2.44  CH.sub.3                                                                          C.sub.2 H.sub.5                                                                  H   H   --COOCH.sub.3                                                                        b.p. 108°/0.02 Torr.                       2.45  C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                  H   H   --COOCH.sub.3                                                                        b.p. 132°/0.09 Torr.                       2.46  CH.sub.3                                                                          Cl H   H   --COOCH.sub.3                                                                        b.p. 115°/0.02 Torr.                       2.47  CH.sub.3                                                                          Br 4-Cl                                                                              H   --COOCH.sub.3                                                                        b.p. 153°/0.008 Torr.                      2.48  CH.sub.3 O                                                                        CH.sub.3                                                                         H   H   --COOCH.sub.3                                                                        b.p. 124°/0.06 Torr.                       2.49  CH.sub.3 O                                                                        Cl H   H   --COOCH.sub.3                                                                        b.p. 148°/0.03 Torr.                       __________________________________________________________________________     The compounds of the formula I can be used by themselves or together with     suitable carriers and/or other additives. Suitable carriers and additives     can be solid or liquid and correspond to the customary substances used in     the art of formulation, for example natural or regenerated mineral     substances, solvents, dispersants, wetting agents, tackifiers, thickeners,     binders or fertilisers. The preparation of these compositions is effected     in known manner by intimately mixing and grinding the constituents.

For application the active substances may take, and be used in, thefollowing forms:

Solid forms: dusts, tracking agents, granules, coated granules,impregnated granules and homogeneous granules.

Liquid forms:

(a) active substance concentrates which are dispersible in water:wettable powders, pastes, emulsions; concentrated solutions.

(b) Solutions; aerosols.

The content of active substance in the above described compositions isbetween 0.1% and 95%.

It will be readily understood that the compounds of the formula I can beused together with other suitable pesticides, for example fungicides,insecticides, acaricides or active substances which influence plantgrowth, in order to adapt them to prevailing circumstances and tobroaden their activity spectrum. For application the active substancesof the formula I can be formulated, for example, as follows:

Dusts: The following substances are used to prepare (a) 5% and (b) a 2%dust:

(a) 5 parts of active substance 95 parts of talc;

(b)

2 parts of active substance

1 part of highly dispersed silicic acid

97 parts of talc.

The active substances are mixed with the carriers and ground and in thisform can be processed to dusts for application.

Granulate: The following substances are used to prepare a 5% granulate:

5 parts of active substances

0.25 parts of epichlorohydrin

0.25 parts of cetyl polyglycol ether

3.50 parts of polyethylene glycol

91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and the mixture isdissolved in 6 parts of acetone. Then polyethylene glycol and cetylpolyglycol ether are added. The resultant solution is sprayed on kaolinand the acetone is evaporated in vacuo. Such a microgranulate isadvantageously used for combating soil fungi.

Wettable powders: The following constituents are used to prepare (a)70%, (b) a 40%, (c) and (d) a 25% and (e) a 10% wettable powder:

(a)

70 parts of active substance

5 parts of sodium dibutyl naphthylsulphonate

3 parts of naphthalenesulphonic acid/phenolsulphonic acid/formaldehydecondensate (3:2:1)

10 parts of kaolin

12 parts of Champagne chalk.

(b)

40 parts of active substance

5 parts of sodium lignin sulphoate

1 part of sodium dibutylnapthalenesulphonic acid

54 parts of silicic acid.

(c)

25 parts of active substance

4.5 parts of calcium lignin sulphonate

1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1)

1.5 parts of sodium dibutylnaphthalenesulphonate

19.5 parts of silicic acid

19.5 parts of Champagne chalk

28.1 parts of kaolin

(d)

25 parts of active substance

2.5 parts of isooctylphenoxy-polyethylene-ethanol

1.7 parts of a Champagne chalk/hydroxyethyl cellulose mixture (1:1)

8.3 parts of sodium aluminium silicate

16.5 parts of kieselguhr

46 parts of kaolin

(e)

10 parts of active substance

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulphates

5 parts of naphthalenesulphonic acid/formaldehyde condensate

82 parts of kaolin.

The active substances are intimately mixed in suitable mixers with theadditives and ground in appropriate mills and rollers. Wettable powdersof excellent wettability and suspension powder are obtained. Thesewettable powders can be diluted with water to give suspensions of thedesired concentration and can be used in particular for leafapplication.

Emulsifiable concentrates: The following substances are used to preparea 25% emulsifiable concentrate:

25 parts of active substance

2.5 parts of epoxidised vegetable oil

10 parts of an alkylarylsulphonate/fatty alcohol polyglycol ethermixture

5 parts of dimethyl formamide

57.5 parts of xylene.

By diluting such a concentrate with water it is possible to prepareemulsions of the desired concentration, which are especially suitablefor leaf application.

EXAMPLE 4 Action on Phytophthora infestans on tomato plants (Ia)Residual preventive action

Tomato plants of the "Roter Gnom" variety are infected when 3 weeks oldwith a zoospore suspension of Phytophthora infestans after they havebeen sprayed with a broth (prepared from the active substance formulatedas a wettable powder) containing 0.05% of active substance, and dried.The plants are then kept for 6 days in a climatic chamber at 18° to 20°C. and high humidity, which is produced by means of an artificial wetfog. After this time typical leaf specks appear. The effectiveness ofthe tested substance is assessed by determining the number and size ofthese specks.

(Ib) Curative Action

"Roter Gnom" tomato plants are sprayed when 3 weeks old with a zoosporesuspension of the fungus and incubated in a climatic chamber at 18° to20° C. and saturated humidity. The humidifying is interrupted after 24hours. After the plants have dried, they are sprayed with a broth whichcontains the active substance formulated as a wettable powder in aconcentration of 0.05%. After the spray coating has dried, the plantsare again kept in the humid chamber for 4 days. The effectiveness of thetested substances is assessed by determining the size and number of thetypical leaf specks which have occurred during this time.

(II) Preventive-systemic action

The active substance is applied as a wettable powder in a concentrationof 0.05% (referred to the volume of the soil) to the surface of the soilof 3 week old "Rotor Gnom" tomatoes in pots. Three days later theunderside of the leaves of the plants are sprayed with a zoosporesuspension of Phytophthora infestans. The plants are then kept in aspray chamber at 18° to 20° C. and saturated humidity for 5 days, afterwhich time typical leaf specks form. The effectiveness of the testedsubstance is assessed by determining the size of and number of thespecks.

In these three tests, the compounds of the formula I effected apronounced leaf-fungicidal action.

Compounds of groups Ib and Id reduce the fungus attack on average tobelow 20%. Compounds of the subformula I' and those of the formulae Ihand Ij inhibit the fungus attack completely or almost completely(0-10%). Infected, untreated tomato plants were used as controls (=100%attack).

EXAMPLE 5 Action on Plasmopara viticola (Bert. et Curt.) (Berl. et deToni) on vines (a) Residual preventive action

Vine cuttings of the variety "Chasselas" were reared in a greenhouse.Three plants in the 10 leaf stage were sprayed with a broth (containing0.05% of active substance) prepared from the active substances andformulated as a wettable powder. After the coating layer had dried, theplants were infected on the underside of the leaves with the sporesuspension of the fungus. The plants were subsequently kept in a humidchamber for 8 days, after which time symptoms of the disease werevisible on the control plants. The effectiveness of the testedsubstances was assessed by determining the number and size of theinfected areas on the treated plants.

(b) Curative action

Vine cuttings of the varity "Chasselas" were reared in a greenhouse andinfected in the 10 leaf stage on the underside of the leaves with aspore suspension of Plasmopora viticola. After they had been kept for 24hours in a humid chamber, the plants were sprayed with a 0.05% brothprepared from a wettable powder of the active substance.

The plants were then kept in a humid chamber for a further 7 days, afterwhich time the symptoms of the disease were visible on the controlplants. The effectiveness of the tested substances was assessed bydetermining the size and number of the infected areas.

In both these tests the compounds of the formula I effected a goodleaf-fungicidal action. The fungus attack on the vines was reduced onaverage to less than 20% in comparison with control plants. Compounds ofthe subgroups Ib and Id as well as those of subformula I' wereparticularly effective. Many of the compounds, for example compounds1.1, 1.2, 1.3, 1.5, 1.6, 1.9, 1.13, 1.15, 1.18, 1.30, 1.34, 1.35, 1.36,1.38, 1.39, 1.40, 1.54, 1.59, 1.60, and also 2.13, 2.20 to 2.25, 2.30,2.31, 2.33, 2.34 and 2.40, control the fungus attack completely oralmost completely (0-5% attack) even when used in active substanceconcentrations of 0.02%.

EXAMPLE 6 Action on Pythium debaryanum on sugar beets (Beta vulgaris)(a) Action after soil application

The fungus is cultivated on sterile oat grains and added to a mixture ofearth and sand. Flower pots are filled with the infected soil in whichsugar beet seeds are then sown. Immediately after sowing, the testpreparations formulated as wettable powders are poured in the form ofaqueous suspensions over the soil (20 ppm of active substance referredto the volume of the soil). The pots are then stood for 2-3 weeks in agreenhouse at 20°-24° C. The soil is kept uniformly moist by gentlyspraying it with water. The emergence of the sugar beet plants as wellas the number of healthy and sick plants are ascertained in evaluatingthe tests.

(b) Action after seed dressing application

The fungus is cultivated on sterile oat grains and added to a mixture ofearth and sand. Flower pots are filled with the infected soil and sugarbeet seeds which have been treated with the test preparations formulatedas seed dressing powders are sown therein (1000 ppm of active substancereferred to the weight of the seeds). The pots are then stood in agreenhouse for 2-3 weeks at 20°-24° C. The soil is kept uniformly moistby gently spraying it with water. The emergence of the sugar beet plantsas well as the number of healthy and sick plants are ascertained.

Under the conditions of both test (a) and test (b), more than 80% of thesugar beet plants emerged after treatment with the active substances ofthe formula I and had a healthy appearance.

The pronounced action of compounds 2.21, 2.22 and 2.33, which completelysuppress a Pythium attack, is to be singled out for particular mention.

EXAMPLE 7 Action on Cercospore arachidicola on ground nut plants(Arachis hypogaea) Residual protective action

Ground nut plants, 10 to 15 cm in height, were sprayed with a spraybroth (containing 0.02% of active substance) prepared from a wettablepowder of the active substance, and 48 hours later infected with aconidia suspension of the fungus. The infected plants were incubated for24 hours at approx. 21° C. and high humidity and subsequently stood in agreenhouse until the occurrence of the typical leaf specks. Theevaluation of the fungicidal action, based on the number and size of thespecks, was made 12 days after the infection.

In comparison with infected, untreated control plants, the fungus attackwas markedly inhibited in plants treated with active compounds of theformula I, in particular when using compounds 1.27, 1.30, 1.53 and 1.56(attack 0-5%).

We claim:
 1. A compound of the formula ##STR66## wherein R₁ represents aC₁ -C₄ -alkyl group, a C₁ -C₄ -alkoxy group or a halogen atom,R₂represents a hydrogen atom, a C₁ -C₃ -alkyl group, a C₁ -C₄ -alkoxygroup or a halogen atom, R₃ represents a hydrogen atom, a C₁ -C₃ -alkylgroup or a halogen atom, R₄ represents a hydrogen atom or a methylgroup, with the proviso that the total number of carbon atoms containedby the substituents R₁, R₂, R₃ and R₄ on the phenyl ring does not exceed8, and X represents ##STR67## R₅ represents --COOR', --COSR' or##STR68## wherein each of R', R" and R'" independently represents amethyl or ethyl group, R₆ and R₇ together with the nitrogen atom towhich they are attached are pyrrolidine, or salts of the compounds ofthe formula I with an inorganic or organic acid.
 2. A compound of theformula I according to claim 1, whereinR₁ represents a methyl group, R₂is in ortho-position to the amino group and represents a methyl or ethylgroup or a chlorine atom, and --X--R₅ represents the group--CH(CH₃)--COOR' or --CH(CH₃)--CO--S--R'.
 3. Compounds of the formula Iaccording to claim 1, whereinR₁ represents a methyl or methoxy group, R₂is in ortho-position to the amino group and represents a methyl or ethylgroup, a chlorine or bromine atom, R₃ represents a hydrogen atom, amethyl group, a chlorine or bromine atom, R₄ represents a hydrogen atomor a methyl group, and --X--R₅ represents the group --CH(CH₃)--COOCH₃ or--CH(CH₃)--COSCH₃.
 4. The compound according to claim 3 which isN-(1'-methoxycarbonyl-ethyl)-N-pyrrolidinoacetyl)-2,6-dimethylaniline.5. A fungicidal composition which contains as active component afungicidally effective amount of of compound of the formula I accordingto claim 1, together with a suitable carrier therefor.
 6. A method ofcontrolling phytophathogenic fungi or of preventing fungus attack, whichcomprises applying to the plants, parts of plants or their environment,a fungicidally effective amount of a compound of the formula I accordingto claim
 1. 7. A method of controlling phytophathogenic fungi or ofpreventing fungus attack, which comprises applying to plants, parts ofplants or their environment, a fungicidally effective amount of acompound according to claim
 3. 8. A method of controllingphytophathogenic fungi or of preventing fungus attack, which comprisesapplying to plants, parts of plants or their environment, a fungicidallyeffective amount of the compound according to claim 4.